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  • 1965-1969  (1,057)
  • 1890-1899
  • 1880-1889
  • 1968  (1,057)
  • Organic Chemistry  (547)
  • Physics  (496)
  • Insulin  (14)
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  • 1965-1969  (1,057)
  • 1890-1899
  • 1880-1889
Year
  • 1
    ISSN: 1432-0428
    Keywords: Insulin ; 3′,5′-AMP phosphodiesterase ; glycogen metabolism ; lipolysis ; insulin secretion ; antilipolytic action of insulin ; glycogen synthesis and insulin ; cyclic adenosine 3′,5′-monophosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'influence de l'insuline sur le métabolisme du glycogène hépatique et sur la lipolyse semble s'exercer par l'intermédiaire d'une diminution de la concentration de 3,′5′-AMP intracellulaire. Onamontré une diminution de la formation de 3′5′-AMP dans le tissu adipeux incubé avec de l'insuline. L'influence de l'insuline sur la dégradation du 3,′5′-AMP est étudiée. — L'activité de la 3,′5′-AMP-phos-phodiestérase (PDE) est diminuée dans le foie, le tissu adipeux et, de façon non-significative, dans le muscle strié des rats qui manquent d'insuline, c-à-d les rats rendus diabétiques par l'alloxane ou les rats privés de nourriture. L'injection intraveineuse d'une faible dose d'insuline (0.5 U/kg) ou la stimulation de la sécrétion d'insuline endogène par une injection de glucose provoquent une augmentation rapide de l'activité de la phosphodiestérase dans ces tissus. 15 min après l'injection d'insuline, l'activité de la phosphodiesterase du foie est augmentée. L'effet maximum est atteint après 30–45 min. L'activité de la phosphodiestérase rénale n'est pas diminuée dans le diabète alloxanique, l'injection d'insuline s'est avérée inefficace.In vitro, l'insuline cristalline a un effet activant sur la phosphodiestérase purifiée du coeur de boeuf. La concentration d'insuline requise pour doubler l'activité de l'enzyme est de l'ordre de 2 · 10−5 M. Le traitement avec actinomycin D empêche la stimulation par l'insuline de la PDE dans le foie. Ceci peut indiquer que l'action de l'insuline sur l'activité de la phosphodiestérase est essentiellement basée sur une synthèse accrue de l'enzyme. A cause de l'influence de la sécrétion d'insuline sur la concentration en 3,′5′-AMP du foie et du tissu adipeux, le métabolisme du glycogène et la lipolyse peuvent s'adapter rapidement à la prise de nourriture.
    Abstract: Zusammenfassung An der Steigerung der Glykogensynthese der Leber und der Verminderung der Lipolyse durch Insulin ist eine Abnahme der 3′,5′-AMP-Konzentration wesentlich beteiligt. Die 3′,5′-AMP-Bildung ist in Fettgewebe, das mit Insulin inkubiert wird, vermindert. Insulin beeinflußt jedoch auch den 3′,5′-AMP-Abbau. -Die 3′,5′-AMP-Phosphodiesterase (PDE)-Aktivität des Fettgewebes, der Leber und, in geringerem Grade, der Skeletmuskulatur ist im Insulinmangel vermindert, d.h. bei alloxandiabetischen oder hungernden Ratten. I.v. Injektion von 0,5 E/kg Insulin oder eine erhöhte Abgabe von Insulin aus dem Pankreas nach Glucoseinjektion führen in diesen Geweben zu einem raschen Anstieg der PDE-Aktivität. Dieser ist in der Leber schon 15 min nach Insulingabe nachweisbar und erreicht nach 30–45 min sein Maximum. In der Niere ist kein Einfluß von Insulin auf die PDE-Aktivität nachweisbar. — Aus Rinderherz isolierte PDE wirdin vitro durch Insulin aktiviert, jedoch werden2 · 10−5 M zur Verdopplung der Aktivität benötigt. Actinomycin D verhindert die Steigerung der Leber-PDE-Aktivität nach Insulininjektion. So kann die Wirkung des Hormons im wesentlichen auf eine gesteigerte PDE-Synthese zurückgeführt werden. — Durch diesen Einfluß der Insulininkretion auf die 3′,5′-AMP-Konzentration in Leber und Fettgewebe können Glykogenstoffwechsel und Lipolyse rasch an die Nahrungsaufnahme angepaßt werden.
    Notes: Summary Influence of insulin on liver glycogen metabolism and on lipolysis appears to be mediated by a decreased intracellular 3′,5′-AMP concentration. Reduced formation of 3′,5′-AMP had been shown in adipose tissue incubated with insulin. The influence of insulin on 3′,5′-AMP degradation has been investigated. — 3′,5′-AMP phosphodiesterase (PDE) activity was reduced in liver, adipose tissue and, insignificantly, in skeletal muscle of insulin deficient, i.e. alloxan diabetic or starved rats. I.V. injection of a low dose of insulin (0.5 U/kg) or stimulation of endogenous insulin secretion by injection of glucose led to a rapid increase of PDE activity in these tissues. 15 min after insulin injection liver PDE activity was increased. The maximal effect occurred after 30–45 min. Renal PDE activity was not decreased in alloxan diabetes, insulin injection has been found ineffective. —In vitro, there was an activating effect of crystalline insulin on PDE purified from beef heart. Insulin concentration required for duplication of enzyme activity was of the order of 2 · 10−5 M. Treatment with actinomycin D nearly prevented stimulation of liver PDE by insulin. This may indicate that the action of insulin on PDE activity is essentially based on an increased enzyme synthesis. — Owing to the influence of insulin secretion on liver and adipose tissue 3′,5′-AMP concentration, glycogen metabolism and lipolysis can be quickly adapted to food intake.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 1-9 
    ISSN: 1432-0428
    Keywords: Human growth hormone ; Growth hormone ; Insulin ; Diabetes mellitus ; Experimental diabetes ; Acromegaly ; Pathogenesis of diabetes mellitus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Il a été démontré récemment que l'hormone de croissance humaine (HGH) joue un rôle prééminent dans la régulation normale de la glycémie. De plus, il est bien connu que l'hormone de croissance peut créer un état semblable au diabète chez l'animal. Chez l'homme, l'injection de HGH ou l'hypersécrétion de l'hormone endogène dans l'acromégalie est suivie d'intolérance au glucose seulement dans 25% des cas. — Dans ce travail nous présentons des données qui mettent l'action dite diabétogène de HGH dans un contexte plus nuancé. Nous suggérons que HGH, bien que diminuant l'utilisation du glucose par les tissus périphériques, n'est pas une substance primairement diabétogène, car l'effet insulinotrope de l'hormone cause une hyperinsulinémie compensatrice, qui à son tour normalise la tolérance au glucose. HGH est diabétogène exclusivement chez les sujets prédiabétiques dont le pancréas est incapable de répondre à l'effet insulinotrope de l'hormone. Chez ces sujets, la diabétogénicité de HGH n'étant pas surmontée par une hyperinsulinémie compensatrice, la tolérance au glucose sera anormale. Ainsi, HGH peut être considérée comme unfacteur additif pour la pathogénèse du diabète sucré, la condition essentielle et primaire étant un état préexistant de prédiabète.
    Abstract: Zusammenfassung Wie kürzlich gezeigt wurde, spielt das menschliche Wachstumshormon (HGH) eine wichtige Rolle bei der Kontrolle der Blutzucker-Homöostase. Ferner ist schon lange bekannt, daß die Verabreichung von Wachstumshormon an Tiere zu einem diabetesähnlichen Zustand führen kann. Beim Menschen löst die Gabe der Substanz oder die Überproduktion des endogenen Hormons bei der Akromegalie nur in etwa 25 % der Fälle eine Glucosetoleranzstörung aus. — In dieser Arbeit werden Resultate beschrieben, die ein detaillierteres Bild der sogenannten diabetogenen Wirkung des HGH vermitteln. Wir möchten annehmen, daß das HGH, obwohl es den peripheren Glucoseverbraueh herabsetzt, kein primär diabetogener Faktor ist, da es über eine Insulin-mehrausschüttung zu einem Hyperinsulinismus führt, der eine normale Glucosetoleranz bewirkt. HGH zeigt Scine diabetogene Wirkung nur bei Prädiabetikern, deren Pankreas den stimulierenden Effekt des Hormons auf die Insulinausschüttung nicht beantworten kann. Bei diesen Personen kann eine Störung der Glucosetoleranz dadurch entstehen, daß die diabetogene Wirkung des HGH nicht durch einen kompensatorischen Hyperinsulinismus ausgeglichen wird. HGH kann daher als ein Zusatzfaktor bei der Diabetesentstehung angesehen werden, deren Hauptvorbedingung jedoch eine schon vorher bestehende prädiabetische Stoffwechselsituation darstellt.
    Notes: Summary Human growth hormone (HGH) has recently been shown to play a prominent role in the control of blood glucose homeostasis. Furthermore, it has long been known that administration of growth hormone in animals can induce a diabetes-like state. In human subjects, exogenous administration of HGH or hypersecretion of the endogenous hormone in acromegaly is accompanied by glucose intolerance in only about 25 per cent of the cases. — In this paper, data are presented which give a more diversified picture of the so-called diabetogenic action of HGH. It is suggested that HGH, although decreasing the peripheral utilization of glucose, is not a primary diabetogenic factor, since its insulinogenic action causes a compensatory hyperinsulinism, with normal glucose tolerance as the result. HGH is diabetogenic only in prediabetic subjects whose pancreas is unable to respond to the insulinogenic effect of the hormone. In such subjects, the diabetogenic action of HGH not being counterbalanced by a compensatory hyperinsulinism, glucose intolerance may result. Thus, HGH may be regarded as anadditional factor for the development of diabetes, the major prerequisite being a preëxisting prediabetic state.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 111-117 
    ISSN: 1432-0428
    Keywords: Insulin ; diabetes ; insulinase ; rat diaphragm ; glycogen synthesis ; RNA turnover ; cell culture ; anti-insulin serum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Peu de progrès conduisant à la compréhension du diabète en termes moléculaires ont été réalisés. La possibilité qu'il existe une modification dans la structure de l'insuline des diabétiques, aussi bien circulante que pancréatique, s'appuie sur trois arguments expérimentaux obtenus au laboratoire des auteurs. — La purification immunochimique de l'insuline circulante de diabétiques jeunes non traités par l'insuline a d'abord conduit à la constatation que cette insuline est relativement résistante à l'action réductrice et protéolytique d'une préparation d'insulinase musculaire. De plus, l'insuline pancréatique, isolée à partir de cinq pancréas diabétiques, s'est avérée d'activité biologique diminuée quant à son pouvoir d'augmenter la synthèse du glycogènein vivo et à sa capacité d'accélérer le “turnover” du R.N.A. en culture tissulaire. — La nature de cette „insuline anormale” et son rôle possible dans la physiopathologie du diabète sont examinés à la lumière de la nécessité de donner une définition spécifique de la modification moléculaire précise.
    Abstract: Zusammenfassung Unsere Kenntnisse über den Diabetes in molekularbiologischer Sicht haben kaum Fortschritte gemacht. Die Möglichkeit, daß das zirkulierende und das Pankreas-Insulin des Diabetikers strukturelle Unterschiede aufweisen, wird durch die Ergebnisse von drei verschiedenen Untersuchungsreihen gestützt, die im Laboratorium der Verfasser durchgeführt wurden. — Immunologisch gereinigtes zirkulierendes Insulin von Diabetikern, die noch kein Insulin erhalten hatten, erwies sich als recht widerstandsfähig gegenüber dem Abbau durch ein Insulinase-Rohextrakt aus Muskelgewebe. Aus den Bauchspeicheldrüsen von 5 Diabetikern gewonnenes Insulin zeigte sowohl in seiner Fähigkeit, die Glycogen-Synthesein vivo, als auch den Ribonucleinsäuren-Umsatz in der Gewebskultur zu stimulieren, eine herabgesetzte biologische Aktivität. — Bei der Diskussion der Natur dieses „abnormen” Insulins und seiner hypothetischen Rolle in der Physiopathologie des Diabetes ergibt sich besonders deutlich, wie dringend erforderlich eine genauere Klärung des in diesem Falle vorliegenden molekularen Umbaus ist.
    Notes: Summary Understanding of diabetes in molecular terms has advanced very little. The possibility that a structural difference exists in the circulating and pancreatic insulin moiety of diabetics is supported by three lines of evidence obtained in the authors' laboratory. — Immunologically purified circulating insulin from diabetic subjects untreated with insulin was noted to be relatively resistant to degradation by a crude muscle insulinase preparation. The pancreatic insulin of five diabetic pancreases was found to have a decreased biological activity in its ability to enhance glycogen synthesisin vivo and in its capacity to stimulate RNA turnover in tissue culture. — The nature of this “abnormal insulin” and its hypothetical role in the physiopathology of diabetes are discussed in the light of the need for a specific definition of the precise molecular change.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 68-70 
    ISSN: 1432-0428
    Keywords: Insulin ; proinsulin ; biosynthesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé Après incubation de tranches de pancréas d'embryon de veau, la leucine-H3 est incorporée dans une fraction protéique qui semble avoir les propriétés d'une “proinsuline”. Cette fraction protéique est de taille supérieure à l'insuline, possède l'immunoréactivité propre à l'insuline, et après traitement limité par la trypsine elle est transformée en un peptide semblable à l'insuline.
    Abstract: Zusammenfassung Die Inkubierung von Dünnschnitten des fötalen Rinder-Pankreas in Gegenwart vom H3- Leucin ergab einen Einbau dieser Amminosäure in eine Eiweißfraktion, die die Eigenschaften eines, Pro-Insulins' aufwies. Das Molekulargewicht dieser Eiweißfraktion war größer als dasjenige des Insulins; sie besaß die Immunreaktivität des Insulins und konnte durch teilweisen Abbau mit Trypsin in ein insulinähnliches Peptid umgewandelt werden.
    Notes: Summary Incubation of fœtal bovine pancreas slices resulted in the incorporation of3H-leucine into a protein fraction which appeared to have the properties of a ‘proinsulin’. This protein fraction was larger in size than insulin, possessed the immunoreactivity of insulin and was converted by limited trypsin treatment to a peptide similar to insulin.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Diabetologia 4 (1968), S. 281-285 
    ISSN: 1432-0428
    Keywords: Insulin ; radioimmunoassay ; bile ; bile acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Résumé L'effet des acides biliaires sur le dosage radioimmunologique de l'insuline a été examiné et les résultats ont montré que les acides biliaires en concentrations physiologiques nuisent à la liaison de l'insuline avec le sérum anti-insulinique. La courbe de dilution de l'insuline immunoréaetive dans la bile de la vésicule biliaire porcine n'était pas parallèle à celle de l'insuline porcine standard. Après extraction de la bile porcine par du sérum antiinsulinique et après dosage de l'extrait, des taux d'insuline plus bas ont été trouvés. Les résultats suggèrent qu'une partie seulement de «l'insuline immunoreactive» de la bile de la vésicule biliaire représente de l'insuline véritable.
    Abstract: Zusammenfassung Die Wirkung von Gallensäuren auf die radio-immunologische Insulinbestimmung wurde untersucht. Aus den Resultaten geht hervor, daß Gallensäuren in physiologischen Konzentrationen zu einer Störung der Insulinbindung an Anti-Insulinserum führen. Die Verdünnungskurve von immunoreaktivem Insulin im Gallensaft aus Schweinegallenblasen verlief nicht parallel zur Standard-Eichkurve von Schweineinsulin. Nach Extraktion der Schweinegalle mit Anti-Insulinserum fanden sich im Extrakt niedrigere Insulinkonzentrationen. Die Ergebnisse deuten darauf hin, daß nur ein Teil des „immunoreaktiven Insulins” in der Blasengalle echtes Insulin ist.
    Notes: Summary The effect of bile acids on the radioimmunoassay of insulin has been investigated, and the results show that bile acids in physiological concentrations interfere with the binding of insulin by anti-insulin serum. The dilution curve of immunoreactive insulin in pig gall-bladder bile was not parallel to that of standard pig insulin. After extraction of pig bile with anti-insulin serum and assay of the extract, lower insulin levels were found. The results suggest that only a part of the “immunoreactive insulin” in gall-bladder bile is genuine insulin.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Pflügers Archiv 301 (1968), S. 254-258 
    ISSN: 1432-2013
    Keywords: Insulin ; Potassium Deficiency ; Membrane Potential ; Rat Diaphragm ; Insulin ; Kaliummangel ; Membranpotential ; Rattenzwerchfell
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung An 102 Zellen des Zwerchfells von insgesamt 7 Ratten mit alimentärem Kaliummangel fanden wir unter dem Einfluß von Insulin (0,1 I.E./ml) eine Depolarisation um 11,2 mV, nämlich von −94,6 (s=±6,4) mV bei insgesamt 100 Zellen auf −83,4 (s=±6,8)mV (p 〈 0,001). Die Kaliumkonzentration in der Inkubationslösung betrug 4,7 (s=±0,29) mval/l. — Ferner steigt die bei kaliumverarmten Tieren erniedrigte intracelluläre Kaliumkonzentration unter Insulineinfluß von 107 (s=±12) mval/lH2O IZR auf 130 (s=±19,8) mval/lH2O IZR an (p〈0,05). Die Befunde sprechen dafür, daß Insulin bei kaliumverarmten Tieren einen Netto-Kaliumeinstrom bewirkt, der eine Abnahme des Membranpotentials zur Folge hat.
    Notes: Summary In 102 single muscle cells of 7 rats with alimentary potassium depletion we found under influence of insulin (0.1 I.U./ml) a depolarisation of 11.2 mV, i.e. from −94.6 (s=±6.4)mV (100 cells) to −83.4 (s=±6.8)mV (p〈0.001). The potassium concentration in the incubation medium was 4.7 (s=±0.29) mequ/l. — In addition we measured under influence of insulin (0.1 I.U./ml) an intracellular potassium concentration of 130 mval/lH2O IZR, which is probably higher than in potassium deficient animals without insulin (p〈0.05). These findings suggest that insulin produces a netto potassium influx in potassium deficient animals, which could explain the depolarisation.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Naunyn-Schmiedeberg's archives of pharmacology 260 (1968), S. 254-268 
    ISSN: 1432-1912
    Keywords: Bilirubin ; Glucuronates ; Insulin ; Liver ; Tolbutamide ; Bilirubin ; Glucuronidsynthese ; Insulin ; Leber ; Tolbutamid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Lebergewebe von Ratten, die mit Tolbutamid, mit anderen blutzuckerwirksamen Sulfonylharnstoffderivaten oder mit Insulin behandelt worden waren, bildet bei Inkubation in vitro mehr Bilirubinglucuronid als das Gewebe unbehandelter Kontrolltiere. Dieser Effekt wurde 2 Std nach der intraperitonealen Injektion der blutzuckersenkenden Stoffe nachgewiesen, er tritt dosisabhängig auf und ist mit der blutzuckersenkenden Wirkung gut korreliert. Ein dem Tolbutamid chemisch verwandtes, jedoch blutzuckerunwirksames Methylsulfonylharnstoffderivat hatte diese Wirkung nicht. Die Steigerung der Glucuronidsynthese ist dadurch bedingt, daß in der Leberzelle während einer Insulin- oder Sulfonylharnstoffhypoglykämie vermehrt aktivierte Glucuronsäure (UDPGA) für die Konjugation bereitgestellt wird. Die Aktivität des für die Konjugationsreaktion verantwortlichen Enzyms, der UDP-Glucuronyltransferase, war unter unseren Versuchsbedingungen nicht verändert. Es fanden sich keine Anhaltspunkte dafür, daß in der Insulin- oder Sulfonylharnstoffhypoglykämie die Bildung von UDPGA aus UDPG beschleunigt erfolgt. Die Aktivität der UDPG-Dehydrogenase war nicht verändert, auch Faktoren, die eine Bildung von UDPGA begünstigen könnten, wie ein erhöhter NAD+/NADH-Quotient und eine gesteigerte ATP-Konzentration im Gewebe, waren nach Tolbutamid nicht nachzuweisen.
    Notes: Summary Liver tissue of rats pretreated with tolbutamide, with other hypoglycaemic sulfonylurea compounds, or with insulin formed more bilirubinglucuronide when incubated in vitro than the tissue of untreated controls. The effect was present two hours after the blood sugar lowering agents had been injected intraperitoneally. It was dose-dependent and well correlated to the hypoglycaemic response. A methylated sulfonylurea compound, which is chemically closely related to tolbutamide but devoid of blood sugar lowering activity failed to show this effect. Glucuronide formation in hypoglycaemia induced by insulin or tolbutamide is increased as more activated glucuronic acid (UDPGA) is made available to the conjugation reaction. There was no change in the activity of the enzyme responsible for glucuronide synthesis, the UDP-glucuronyl-transferase, in our experiments. There was no indication that the formation of UDPGA from UDPG was accelerated by insulin or sulfonylureas. There was no change in the activity of the hepatic UDPG-dehydrogenase. Factors which could favour the formation of UDPGA such as an increased NAD+/NADH ratio or an elevated ATP concentration in the tissue were not present following tolbutamide.
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 5 (1968), S. 279-298 
    ISSN: 1432-5233
    Keywords: Choline ; Clinical situation (diabetes) ; Glucagon ; Growth hormone ; Heparin ; Histamine ; Insulin ; Insulinemia ; Night vision ; Pro-insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Alors que mon intérêt pour l'insuline a été pratiquement continu depuis déjà sa découverte, il y a eu des périodes pendant lesquelles mon attention s'est concentrée sur la coline, l'histamine et l'héparine. Pendant les années de guerre, les sujets de recherche ont été naturellement très différents. Les points importants dans le développement de l'insuline, du point de vue chimique, ont été sa purification, cristallisation, détermination de la structure et synthèse. Les physiologistes ont été fascinés par les études regardant le point et le mécanisme d'action de l'insuline. On a appris beaucoup quant à l'action sur grand nombre de tissus différents et l'insuline se montra être la principale hormone anabolique. Les développements cliniques ne sont mentionnés que brièvement car mes intérêts personnels de recherche ont été exclusivement expérimentaux.
    Abstract: Resumen Mientras mi interés para insulina fue prácticamente continuo desde su descubrimiento, hubo períodos en que mi atención se concentró sobre colina, histamina y heparina. Durante los años de la guerra, los temas de investigación fueron naturalmente muy diferentes. Los puntos fundamentales en el desarrollo de la insulina desde el punto de vista químico, fueron su purificación, cristalización, determinación de la estructura y síntesis. Los fisiólogos fueron cautivados por los estudios sobre el punto y el mecanismo de acción de la insulina. Mucho se aprendió acerca de la acción sobre muchos tejidos diferentes y la insulina demostró ser la hormona anabólica principal. Los desarrollos clínicos se mencionan sólo brevemente pues mis intereses personales de investigación han sido exclusivamente experimentales.
    Notes: Riassunto Mentre il mio interesse per l'insulina è stato praticamente continuo sin dalla sua scoperta, ci sono stati periodi nei quali la mia attenzione si concentrò sulla colina, istamina ed eparina. Durante gli anni della guerra, i temi di ricerca furono naturalmente molto diversi. I momenti culminanti nello sviluppo dell'insulina, dal punto di vista chimico, furono la sua purificazione, cristallizzazione, determinazione della struttura e sintesi. I fisiologi sono stati affascinati dagli studi circa il punto ed il meccanismo di azione dell'insulina. Molto è stato appreso intorno all'azione su molti tessuti differenti e l'insulina dimostrò di essere l'ormone anabolico principale. Gli sviluppi clinici sono menzionati solo brevemente poichè i miei personali interessi di ricerca sono stati esclusivamente sperimentali.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Acta diabetologica 5 (1968), S. 347-363 
    ISSN: 1432-5233
    Keywords: Diabetes mellitus ; Gel-filtration ; Insulin ; 125J-insulin-plasma complex
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. ont étudié la capacité des protéines plasmatiques de lier l'insuline125J avec la méthode de filtration surgel. Le fractionnement parSephadex G-100 a démontré que seulement le 10 % de l'insuline marquée était lié par le protéines plasmatiques des sujets sains, des femmes gravides et des diabétiques non traités. Un pourcentage d'insuline beaucoup plus élevé était liée par les protéines plasmatiques dans des sujets que étaient traités precédemment avec de l'insuline bovine, tandis que le degrée de la liason était tres élevé dans les diabétiques insulino-résistants. De recherches avecSephadex G-200 ont demontré que, après une courte période d'insulinothérapie, le complexe insuline-protéine migrait avec les globulines 19 S. Après une insulinothérapie prolongée et dans les cas insulino-résistants la plus grande partie de l'insuline marquée liée aux protéines était élui avec les globulines 7 S. Le phénomène est attribué à l'action des anticorps anti-insuline bovine.
    Abstract: Resumen La capacidad que poseen las proteínas para ligar la insulina marcada con125J se estudió mediante el método de filtración engel. El fraccionamiento medianteSephadex G-100 demostró que solamente el 10 % de la insulina marcada estaba ligada por las proteínas plasmáticas de sujetos sanos, de mujeres embarazadas y de pacientes diabéticos no tratados. Un porcentaje de insulina notablemente superior estaba ligado por las proteínas plasmáticas en pacientes que anteriormente habían sido tratados con insulina bovina, mientras el grado de enlace se volvía muy elevado en los diabéticos resistentes a la insulina. Experimentos realizados conSephadex G-200 demostraron que después de un breve tratamiento insulínico, el complejo insulina-proteína migraba con las globulinas 19 S. Después de un prolongado tratamiento insulínico y en los casos resistentes a la insulina, la mayor parte de la insulina marcada con las proteínas resultaba eluida con las globulinas 7 S. El fenómeno, discutido detalladamente, se atribuye a la acción de los anticuerpos anti-insulina bovina.
    Notes: Riassunto La capacità delle proteine plasmatiche di legare l'insulina marcata con125J è stata studiata mediante il metodo di filtrazione sugel. Il frazionamento medianteSephadex G-100 ha dimostrato che soltanto il 10% dell'insulina marcata era legato dalle proteine plasmatiche di soggetti sani, di donne gravide e di pazienti diabetici non trattati. Una percentuale di insulina notevolmente superiore era legata dalle proteine plasmatiche in pazienti che erano stati precedentemente trattati con insulina bovina, mentre il grado di legame diveniva molto elevato nei diabetici insulino-resistenti. Esperimenti eseguiti conSephadex G-200 hanno dimostrato che, dopo una breve terapia insulinica, il complesso insulina-proteina migrava con le globuline 19 S. Dopo prolungata terapia insulinica e nei casi insulino-resistenti la maggior parte dell'insulina marcata legata alle proteine era eluita con le globuline 7 S. Il fenomeno, discusso nei particolari, è attribuito all'azione degli anticorpi anti-insulina bovina.
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  • 10
    ISSN: 1432-5233
    Keywords: Bovine insulin ; Insulin ; Insulin antibodies ; Insulin resistance ; Pork insulin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. présentent les résultats obtenus avec une méthode très simple pour la recherche des anticorps anti-insuline, basée sur l'emploi d'insuline I125 ou I131 et sur la précipitation avec alcool absolu du complexe antigène-anticorp. Les anticorps anti-insuline ont été fréquemment observés seulement dans des sujets diabétiques déjà soumis à traitement avec insuline. Un taux élevé d'anticorps anti-insuline s'accompagne à une diminution de la sensibilité à l'insuline (0,1 U/kg i.v.).
    Abstract: Resumen Se expresan los resultados obtenidos con el empleo de un método que puede ser ejecutado en forma my simple, para la investigación de anticuerpos anti-insulina; el método se basa sobre el empleo de insulina I125 o I131; y sobre la precipitación sucesiva con alcohol absoluto del complejo antígeno-anticuerpo. Los anticuerpos anti-insulina han sido hallados con mucha frecuencia solamente en pacientes diabéticos, que recibían tratamiento insulínico. Un título elevado de anticuerpos antiinsulina se asocia a una disminución sensible de la sensibilidad a la insulina (0,1 U/kg i.v.).
    Notes: Riassunto Vengono presentati i risultati ottenuti con l'impiego di una metodica di semplice esecuzione per la ricerca di anticorpi anti-insulina, basata sull'impiego di insulina I125 o I131 e sulla successiva precipitazione con alcool assoluto del complesso antigene-anticorpo. Gli anticorpi anti-insulina sono stati riscontrati con grande frequenza solo in pazienti diabetici già sottoposti a trattamento insulinico. Un elevato titolo di anticorpi anti-insulina si associa ad una diminuzione marcata della sensibilità all'insulina (0,1 U/kg i.v.).
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  • 11
    ISSN: 1432-5233
    Keywords: Insulin ; Insulin antibodies ; Insulin binding properties of serum ; Insulin therapy ; Serum proteins
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Les AA. ont observé que le sérum d'un sujet normal et celui d'un diabétique, jamais traité avec insuline, ont la possibilité de lier l'insuline dans la même mesure. Dans certains sérums, soit du sujet normal soit du diabétique, est présente une activité de liaison de l'insuline supérieure aux taux normaux plus élevés; cette activité diminue après administration de µU 500 d'insuline bovine. Les AA. présentent leurs considérations à propos de ce phénomène.
    Abstract: Resumen Los AA. observan que los sueros del individuo normal y del diabético nunca tratado con insulina poseen propiedades insulino-ligantes de entidad análoga. En algunos sueros — ya del sujeto normal, ya del diabético — está presente una actividad insulino-ligante superior a los valores máximos normales, que disminuye luego de haber agregado µU 500 de insulina bovina. Los AA. hacen algunas consideraciones interpretativas de tal fenómeno.
    Notes: Riassunto Gli AA. rilevano che i sieri dell'individuo normale e del diabetico mai trattato con insulina sono provvisti di proprietà insulino-legante di entità analoga. In alcuni sieri, sia del soggetto normale che del diabetico, è presente un'attività insulino-legante superiore ai valori massimi normali, che diminuisce dopo aggiunta di µU 500 di insulina bovina. Gli AA. fanno alcune considerazioni interpretative su tale fenomeno.
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  • 12
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    Acta diabetologica 5 (1968), S. 499-512 
    ISSN: 1432-5233
    Keywords: Entero-insular axis ; Gastrin ; Glucagon ; Gut hormones ; Insulin ; Pancreozymin ; Secretin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Resume Des préparations hautement purifiées de gastrine, sécrétine et pancréozymine ont été injectées par voie endoportale chez des chiens anesthésiés, en vue d'examiner les influences possibles des hormones gastro-intestinales sur la sécrétion des îlots de Langerhans. On a vu que les trois hormones provoquent une augmentation immédiate de la concentration d'insuline dans la veine pancréatico-duodénale. L'effet de la gastrine sur la libération d'insuline était insignificant quantitativement, tandis que celui de la sécrétine était plus important et de plus grande durée; cependant la pancréozymine semblait être le stimulant le plus puissant et déterminer en outre une augmentation parallèle de la sécrétion pancréatique de glucagon. On a démontré de plus que la pancréozymine augmentait la réponse tant de l'insuline que du glucagon à l'hyperaminoacidémie. On a observé que l'administration intraduodénale d'acides aminés, qui représente notoirement la stimulation la plus puissante de la pancréozymine endogène, est en mesure de déterminer une libération plus grande et plus rapide d'insuline et de glucagon par rapport à l'administration intraveineuse d'acides aminés, ce qui fait supposer que la pancréozymine endogène joue un rôle physiologique lorsque la réponse de l'hormone des cellules insulaires aux acides aminés ingérés est augmentée. Le facteur physiologique qui augmente la réponse insulaire au glucose ingéré reste toutefois inconnu.
    Abstract: Resumen Medicamentos altamente purificados de gastrina, secretina y pancreozimina han sido inyectados por via intraportal a perros anestesiados, con el fin de examinar las posibles influencias de las hormonas gastro-intestinales sobre la secreción de las hormonas de las islas de Langerhans. Se ha notado que las tres hormonas producen aumento inmediato de la concentración de insulina en la vena pancreática-duodenal. El efecto de la gastrina sobre la liberación de insulina era insignificante cuantitativamente, mientras el de la secretina era apreciable y de mayor duración; sin embargo, parecía que la pancreozimina fuese el estimulante más potente y que además determinava aumento paralelo de la secreción pancreática de glucagón. Además se ha demostrado que la pancreozimina aumentava la respuesta, ya de la insulina, ya del glucagón, a la hiperaminoacidemia. La administración intraduodenal de aminoácidos, que representa notoriamente el más potente estímulo de la pancreozimina endógena, está en grado de provocar una liberación mayor y más rápida de insulina y glucagón, que la administración intravenosa de aminoácidos; cosa que hace pensar que la pancreozimina endógena ejerce un papel fisiológico cuando aumenta la respuesta de la hormona de las células de las islas a los aminoácidos ingeridos. Sin embargo, el factor fisiológico que aumenta la respuesta insular a la glucosa ingerida, queda desconocido.
    Notes: Riassunto Preparati altamente purificati di gastrina, secretina e pancreozimina sono stati iniettati per via endoportale in cani anestetizzati, allo scopo di esaminare le possibili influenze degli ormoni gastro-intestinali sulla secrezione degli ormoni delle isole di Langerhans. Si è riscontrato che tutti e tre gli ormoni provocano un immediato aumento della concentrazione di insulina nella vena pancreatico-duodenale. L'effetto della gastrina sulla liberazione di insulina era quantitativamente insignificante, mentre quello della secretina era più rilevante e di maggiore durata; tuttavia sembrava che la pancreozimina fosse il più potente stimolatore e che inoltre determinasse un aumento parallelo della secrezione pancreatica di glucagone. Per di più si è dimostrato che la pancreozimina aumentava la risposta sia dell'insulina che del glucagone alla iperaminoacidemia. La somministrazione intraduodenale di aminoacidi, che rappresenta notoriamente la più potente stimolazione della pancreozimina endogena, è stata riscontrata in grado di determinare una liberazione maggiore e più rapida di insulina e di glucagone rispetto alla somministrazione endovenosa di aminoacidi, il che fa pensare che la pancreozimina endogena svolga un ruolo fisiologico nell'aumentare la risposta dell'ormone delle cellule insulari agli aminoacidi ingeriti. Tuttavia il fattore fisiologico che aumenta la risposta insulare al glucosio ingerito rimane sconosciuto.
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  • 13
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    Clinical and experimental medicine 148 (1968), S. 22-27 
    ISSN: 1591-9528
    Keywords: Insulin ; Hypoglycemia ; Xylitol ; Insulin ; Hypoglykämie ; Xylit
    Source: Springer Online Journal Archives 1860-2000
    Topics: Medicine
    Description / Table of Contents: Zusammenfassung Bei Kaninchen, Meerschweinchen, Mäusen und Ratten wurde der Einfluß von Xylit auf die Insulinhypoglykämie untersucht. Es zeigte sich, daß Xylit die durch große intravenöse Insulindosen hervorgerufenen neurogenen Störungen (Lähmungserscheinungen, Krämpfe) zu beseitigen bzw. zu verhüten vermag. Gleichzeitig kommt es zu einem Wiederanstieg der Glucosekonzentration im Blut. Die möglichen Mechanismen dieser Wirkung werden diskutiert.
    Notes: Summary The influence of xylitol on insulin-induced hypoglycemia was studied in rabbits, guinea pigs, mice, and rats. Relief of hypoglycemia and the concomitant disturbances of the nervous system was observed following the injection of xylitol. The possible mechanisms of this action are discussed.
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  • 14
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 91-109 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: From the sedimentation-diffusion equilibria of some polymer solutions the average molecular weights M̄n, M̄w, M̄z, and M̄z+1 have been determined in different ways. In particular, the applicability of Fujita's method, which utilizes concentration gradient values at the midpoint of the solution column at a number of rotor speeds, was examined. It appears that if the gradients at some other places in the column are also used, a smaller range of rotor speeds suffices. This method is generally applicable for determining the average molecular weights specified above.
    Additional Material: 11 Ill.
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  • 15
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 129-140 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The viscoelastic properties of monodisperse poly-α-methylstyrenes of molecular weights of 4 × 104 to 50 × 104 were studied by the tensile stress-relaxation method. The relaxation-time spectra as well as the steady-flow viscosity, the steady-state compliance, the maximum relaxation time, and the modulus associated with the maximum relaxation time were determined. The molecular weight dependences of these quantities were compared with the theory of Rouse and Bueche as modified by Ferry, Landel, and Williams, as well as with data on other polymers reported in the literature.
    Additional Material: 9 Ill.
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  • 16
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 231-240 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The morphological character of the surface region of polyethylene has been considered with respect to adhesion and adhesive joint strength. By melting polyethylene onto a high-energy surface (e.g., aluminum) we have provided for extensive nucleation and the formation of a transcrystalline region in the polymer. Dissolution of the metal rather than peeling the metal from the polymer leaves the surface region of the polymer intact. The polymer sheet is now amenable to conventional adhesive bonding and forms a strong adhesive joint. We conclude from this study that the occurrence of the normal weak boundary layer is a consequence of the morphology of the surface region of the material and is, therefore, influenced by the method of preparation.
    Additional Material: 6 Ill.
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  • 17
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular structures of chlorinated poly(vinyl chloride) and polybutadiene have been studied by high resolution NMR. The spectra of the chlorinated polymers give broad signals. New peaks appear in the lower fields of the —CH2— and —CHCl— groups with increasing chlorine content. The chlorination of poly(vinyl chloride) takes place predominantly on —CH2— rather than on —CHCl—, e.g., a 70% chlorinated polymer has about 10 mole-% of —CCl2— groups. Polybutadiene reacts first with chlorine by addition to give a head-to-head poly(vinyl chloride), and then the substitution of the hydrogen atom takes place. Chlorinated polybutadiene with 70% Cl has about 18 mole-% of —CCl2—. The multiplets characteristic of spin-spin couplings in the spectrum of the original poly(vinyl chloride) are still observed in that of the highly chlorinated product. This fact shows that a considerable number of poly(vinyl chloride) sequences of certain lengths persist in the highly chlorinated polymer.
    Additional Material: 4 Ill.
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  • 18
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 281-288 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: For polyethylene fibers, orientation parameters of the form 〈cos2 φ〉 were calculated from traces obtained with an x-ray diffractometer equipped with an orientation integrator. The angle φ is that which a crystal or molecular axis makes with the fiber axis. Traces over a continuous range of diffraction angle were obtained for (2/π)Iav, and also the weighted averages (2/π)Iav 〈cos2φ〉 and (2/π)Iav 〈sin2φ〉, where Iav is the intensity averaged over all orientations. The orientation for the crystal a, b, and c axes were determined from area measurements of the {110} and {200} lines, and the orientation parameter for the molecular axis in the amorphous phase was determined from area measurements of the amorphous halos. An undrawn fiber showed a slight a and c axis orientation along the fiber axis, and a slight transverse orientation of the b axis and the molecular axis. For a highly drawn fiber the orientation parameter for the c axis was 0.98 and for the molecular axis 0.65. The degree of crystallinity, measured from the (2/π)Iav versus 2θ traces, were 66.1% and 73.3% for the undrawn and drawn fiber, respectively.
    Additional Material: 3 Ill.
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  • 19
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 301-301 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 20
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 383-406 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complete fractionations into 5, 10, and 20 fractions were calculated by a numerical method based on the Flory-Huggins theory in order to evaluate various procedures for determining the molecular weight distribution from fractionation data. If the initial distributions are wide, the differential distribution cannot be accurately reconstructed, not even if each fraction is characterized by two average molecular weights (instead of one, as is customary). In addition to this inadequacy in the evaluation procedure there are the experimental errors which further detract from the accuracy of the result. The integral distribution can, in some cases, be approximated fairly well by means of the Schulz method, provided that the polymer is separated into many fractions with narrow distributions. However, the integral distribution thus obtained does not reflect details in the differential distribution. Polymer fractionation does not appear to be a suitable procedure for accurate determination of the differential distribution. From the assembled material, a thermodynamic method has been derived which seems to hold out better prospects. It should enable the differential distribution to be directly determined from a detailed analysis of the liquid-liquid phase relationships, provided the free energy of mixing function of the system is known.
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  • 21
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 289-293 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 22
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 463-477 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The conductivity of dry poly(hexamethylene adipamide) (nylon 66) was measured as a function of time and temperature. Three temperature ranges were observed in which the time dependence of conductivity differed: (a) below 80°C. the conductivity decreased continuously with time; (b) between 80°C. and 110°C. the conductivity remained constant over long periods; (c) above 120°C. a continuous decrease in conductivity was again observed. In other experiments the volume of gas evolved from the nylon film was measured under continuous potential and compared with the total current passed through the sample. It was observed that above 120°C. the gas evolved corresponded to about one-half the volume calculated if the conduction process involved only protons. Below 120°C. the gas evolved corresponded to an increasingly small fraction of the total current until below 90°C. no evolution of gas was observed. This suggests that at temperatures above 120°C. conduction involves the transport of both protons and electrons, whereas at lower temperatures it is electronic. Mechanisms of conduction are discussed.
    Additional Material: 7 Ill.
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  • 23
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 509-516 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Acid hydrolysis of a stereoblock poly(methyl methacrylate) sample leads to a mixture of isotactic and syndiotactic poly(methacrylic acid) which can be separated by electrophoresis. The experiment confirms the stereochemical identity between the so-called “stereoblock” poly(methyl methacrylate) and the stereocomplex which syndiotactic and isotactic poly(methyl methacrylate) form in the ratio 2:1. A possible mechanism of replica polymerization is suggested to account for this effect.
    Additional Material: 3 Ill.
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  • 24
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 407-420 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electrical conductivities in vacuo of poly(ethylene oxide) and two higher olefin oxide polymers have been found to be ∼9 orders higher than for other saturated organic polymers. The possibility of ionic transport resulting from the presence of impurities (including water) has been eliminated, and it is proposed that an inherent ionic process is operative, involving the generation of protons and then subsequent transport by a handing-on process. The two general requirements are the presence of proton-accepting atoms (in this case oxygen) in the polymer chains; and proximity to the melting point to ensure adequate chain-mobility. These requirements are met by poly(ethylene oxide), poly(trimethylene oxide), and poly(tetramethylene oxide), which are all close to their melting points at room temperature. poly(methylene oxide), with a melting point of ∼180°C., on the other hand, has the low conductivity of a typical insulator.
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  • 25
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 457-462 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymers containing dynamically isolated polymethylene segments of various lengths were obtained from the reaction of bisphenol-A-diglycidyl ether with α,ω-diamines. On the basis of the mechanical damping data of these polymers, it was established that the shortest polymethylene segment to show the -125°C. γ dispersion, characteristic of polyethylene, must consist of at least five carbon atoms.
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  • 26
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 499-508 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The theta temperature of poly-α-methylstyrene in cyclohexane has been found to vary with the stereostructure of the polymer. The observed values range from 305.5°K. for highly syndiotactic material (0.95 syndiotactic diads) to 310.0°K. for anio ically polymerized samples (0.67 syndiotactic diads). Results indicate that the unperturbed dimensions of the polymer increase with increasing isotacticity of the chain, whereas the entropy parameter ψ1, measured in cyclohexane, decreased as the structure became more isotactic. Measurements of the second virial coefficient in toluene showed an increasing interaction with the solvent as the polymer became more syndiotactic.
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  • 27
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1177-1182 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: At present the widely used model for explaining viscoelastic and dielectric properties of polymer solutions is that of Rouse and Bueche. Here the polymer molecule is considered as an array of Gaussian subunits, each of which acts as an entropy spring. The motion of these segments is damped by the viscous drag of the surrounding solvent (RB model). An alternative model is presented, in which the segments are torsional oscillators consisting of two or three backbone links, and the damping is due to hindered internal rotation (DTO model). The mathematical treatment of these two models is essentially identical, but the physical interpretation of the constants used is very different. The DTO model has previously been applied by one of us to the interpretation of viscoelastic data. It is here applied to the interpretation of dielectric loss data. It is shown that dielectric measurements in dilute solution should very readily discriminate between the two approaches. Finally it is shown that the relaxation time computed from the DTO model is in closer agreement with published NMR data on poly(propylene oxide) 2025, than is the RB relaxation time. The postulates of the DTO model appear to be confirmed for this low molecular weight polymer. An even more sensitive distinction should be available by studies of the relaxation time as a function of polymer concentration.
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  • 28
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1203-1206 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 4 Ill.
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  • 29
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    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 895-911 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The incorporation of comonomers bearing functional groups yields butadiene copolymers capable of hydrogen bonding. Three such butadiene-based materials were studied: methacrylic acid copolymers, 2-methyl-5-vinylpyridine copolymers, and stoichiometric mixtures of the acidic and basic copolymers. The elastic effects of intermolecular hydrogen bonding were determined by comparing the simple weighted average of the moduli of the parent copolymers with the observed modulus of their stoichiometric mixture. The results show that measurable increases in the moduli of the mixtures persist even above the glass temperature Tg, which is itself elevated in the mixtures. These increases may be treated as temperature-dependent temporary crosslinks.
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  • 30
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Styrene and maleic anhydride were copolymerized in benzene. The whole polymer thus obtained was fractionated with acetone and petroleum ether as the solvent and precipitant, respectively. The viscosities and osmotic pressures of the fractions were determined in tetrahydrofuran. The relation between the intrinsic viscosity and the molecular weight, [η] = 5.07 × 10-5 M̄n0.81, was obtained in tetrahydrofuran. The unperturbed mean square end-to-end distance was estimated by the Stockmayer-Fixman equation. A theoretical equation for the mean square end-to-end distance for a chain of repeating units of different bond lengths a and b with a fixed valence angle θ and without restriction of internal rotation was presented and applied to this copolymer. In addition, the equation of the mean-square end-to-end distance derived by Wall for trans-polyisoprene without rotational restriction was modified for application to this copolymer. The result evaluated with our equation was about 26% smaller than that from the modified Wall equation. A steric parameter for the present copolymer is defined and discussed in comparison with those of polystyrenesulfone and polystyrene.
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  • 31
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1083-1091 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements have been made of the anisotropy of viscoelastic behavior in cold-drawn low-density and high-density polyethylene sheets. In the low-density polymer the β transition was shown to be highly anisotropic, maximum losses corresponding to shear on planes containing the axis of drawing and on planes perpendicular to this axis. In high-density polyethylene the α transition shows anisotropy.
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  • 32
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1141-1148 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The thermodynamic properties of crystalline and amorphous poly(2,6-dimethyl-1,4-phenylene ether) (PPORegistered trademark of General Electric Company. polymer, General Electric Co.) have been studied calorimetrically between 80 and 570°K. The calculated configurational entropy of this polymer, of similar magnitude to other glass-forming liquids, is consistent with the combination of an unusually high ratio of Tg/Tm, and a low melting entropy.
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  • 33
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1149-1160 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A method for the theoretical analysis of branching in radical polymerization is presented which includes the dynamics of the process. In particular, the method is applied to a polymerization that occurs by decomposition of initiator, propagation, termination by radical combination, and chain transfer with polymer. By a numerical solution of the kinetic equations (suitably transformed), the time dependence of the number-average degree of polymerization (DP), the weight-average DP, the mean number of branches, and the monomer conversion are obtained. The parameters of the process, that is the rate coefficients and initial concentrations, have the following effects: (1) An increase in the chain transfer coefficient increases the ratio of weight-average to number-average Xw/Xn and the mean number of branches Xb, but does not change the number-average Xn. (2) For a given value of the chain transfer coefficient, a change in the parameters of the process such that Xn increases, causes Xw/Xn and Xb to increase also. (3) Chain transfer with polymer seems to produce relatively few polymer molecules having many branches and a large number of smaller polymer molecules having no branches; consequently, the polymer size (or molecular weight) distribution broadens.
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  • 34
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 825-831 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Extended chain crystals of polyoxymethylene were irradiated with x-rays of about 105 r./min. An immediate decrease in superheating on melting was noted. After 90 min. of irradiation the melting point level, refractive indices, and density also decreased. After 480 min. the DTA melting peak at a heating rate of 20°C./min. had decreased 25°C., the melting point decreased about 18°C., and the density calculated from refractive indices decreased 0.031 g./cm.-3. These effects are interpreted as indication of chain scission and formation of amorphous defects.
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  • 35
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 871-883 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The following measurements were carried out on the melts of two samples of polypropylene, one with a narrow and one with a broad molecular weight distribution: viscosity in steady shear flow, dynamic storage and loss moduli, total normal thrust in cone-and-plate apparatus, and flow birefringence. The validity of various theoretical interrelations between the measured quantities is checked. The influence of molecular weight distribution is qualitatively discussed.
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  • 36
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 913-919 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical lability of intermolecular hydrogen bonds in stoichiometric mixtures of acidic and basic butadiene copolymers has been studied by both infrared and mechanical methods. Comparison is made between the weight-averaged E(t) and H(τ) spectra of the parent copolymers and those of the mixed copolymers. The results indicate that the maximum contributions of bond-interchange relaxation migrate to shorter times as the concentration of bonding groups increases.
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  • 37
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 933-946 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical lability of quadrupolar links in cationic and anionic polyelectrolytes and of ion-pair links in mixed polyelectrolytes is investigated in terms of deviations from the WLF viscoelastic theory. The behavior of E(t), log AT, and Evisc indicate that the quadrupolar links do not interchange below the second transition Tt* found in these materials. The blended polyelectrolytes exhibit low yields of the desired ion pair linking and have transitions characteristic of quadrupolar migration of the unreacted polyelectrolytes.
    Additional Material: 17 Ill.
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  • 38
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 953-960 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A series of well-characterized polyamic acids from pyromellitic dianhydride and 4,4′-diaminodiphenyl ether of systematically varied molecular weight and known molecular weight distribution were chemically converted to polyimide films under regulated conditions. The films were essentially noncrystalline, of moderate orientation, and soluble in concentrated sulfuric acid. The mechanical properties of the films varied sigmoidally with the solution properties of the precursor. Molecular weights were derived for the onset of mechanical strength and limiting property values are given. The relations between film properties and molecular structural parameters suggest that cyclization probably occurs here with little contribution from crosslinking, degradation, or other side reactions which would appreciably alter molecular weight and molecular weight distribution.
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  • 39
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1593-1606 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gum arabic was found to have an osmotic molecular weight of 250,000, in agreement with earlier determinations. A molecular weight of 365,000 was found by light scattering, somewhat higher than obtained earlier by sedimentation equilibrium analysis but lower than light-scattering values reported by other investigators. The M̄w/Mn ratio, 1.46, is quite low in gum arabic. The angular dependence of light scattering exhibited the upward curvature to be expected of a spherical molecule and a radius of gyration of about 100 A. or less, as estimated from a Zimm plot. Fractionation of the original gum arabic was done by precipitation of a 0.5% solution in aqueous 0.5% NaCl with acetone. Comparison of the curves of viscosity versus molecular weight and the estimated radius of gyration shows that the hydrodynamic volume is less than that of branched dextran of similar molecular weight. The electroviscous effects for gum arabic in aqueous solution were shown by reduced viscosity curves at various acidities and in salt. The degree of dissociation was calculated for each pH level. The minimum intrinsic viscosity was found in 0.04N HCl where the degree of dissociation at pH 1.5 was found to be 0.049. When the acidity was increased, further reduction in viscosity was found to be negligible. Routine determination of the viscosity and molecular weight of the fractions was done in 0.35M NaCl at pH 10 to which 0.25% of the sodium salt of ethylenediaminetetraacetic acid was added as a sequestrant. The intrinsic viscosity in this solvent was nearly as low as in 0.04N HCl. Light-scattering dissymmetries in water and in 0.35M NaCl plus EDTA at pH 10 were similar, 1.13 and 1.09, respectively, which showed that actual expansion of the macroion is not the cause of the large increase in viscosity of gum arabic when the ionic strength of the solvent is reduced. Periodate oxidation of the polymer confirmed the existence of a 1-3-linked backbone of galactose. Subsequent treatment of the oxidized polymer with alkali reduced the osmotic molecular weight to 45,000 but failed to remove oxidized side branches. The oxidized polymer was fractionated by gel permeation chromatography and the intrinsie viscosity-molecular weight relation compared with relations for fractions of the unoxidized polymer and for other branched and crosslinked polymers.
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  • 40
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1051-1063 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The energy component of the stress has been determined for poly(vinyl alcohol) networks in swelling equilibrium with a series of water-ethylene glycol compositions. The data are analyzed by using the equations describing the thermoelasticity of networks in swelling equilibrium. The ratio fe/f of the energy component to the total force, as calculated from these equations, varies systematically with diluent composition but is independent of elongation in a given diluent. For a network crosslinked by terephthalaldehyde, fe/f varied from -0.33 to -0.42 as the diluent composition was changed from pure water to 20% ethylene glycol. Similar effects were found in a network crosslinked by formaldehyde. It is not yet certain whether this effect represents a real solvent dependence of fe/f or a failure of the equation of state to account for the effect of composition changes on the force.
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  • 41
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1689-1703 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Stress-induced crystallization in a rapidly stretched natural rubber gum vulcanizate has been studied using thermal techniques to follow the development of crystallinity. A special-purpose analog computer has been assembled and used on-line to process the thermal and mechanical data obtained in high speed tensile testing. Roughly first-order room temperature crystallization kinetics curves were obtained having time constants of 50-60 msec in the range of 400-540% extension. While the rate of this rapid, presumably primary crystallization appears rather insensitive to elongation in this limited range, the extent of crystallization at 400 msec increases smoothly from zero at 340% elongation to around 18% at 540% elongation. It is shown that our high-speed tensile tester can stretch this vulcanizate fast enough that most of the crystallization takes place after extension has been completed. Stress-strain curves obtained at this high rate are compared with those obtained at lower rates where crystallization takes place during the stretching.
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  • 42
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1759-1772 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Experimental evidence concerning the dependence of the intrinsic viscosity [η] on molecular weight M in the low molecular weight range (from oligomers to M = 5 × 104) has been collected in a variety of solvents for about ten polymers, i.e., polyethylene, poly(ethylene oxide), poly(propylene oxide), polydimethylsiloxane, polyisobutylene, poly(vinylacetate), poly(methyl methacrylate), polystyrene, poly-α-methylstyrene, and some cellulose derivatives. In theta solvents, the constancy of the ratio [η]Θ/M0.5 extends down to values of M much lower than those predicted by current hydrodynamic theories. In good solvents, and on decreasing M, the polymers examined, with the exception of polyethylene and some cellulose derivatives, show a decrease in the exponent a of the Mark-Houwink equation [η] = KMa. This upward curvature gives rise to the existence of a more or less extended linear region where the equation [η] = K0M0.5 is obeyed. Below the linear range, i.e., for even shorter chains, the exponent a can increase, i.e., polydimethylsiloxane, or decrease below 0.5, i.e., poly(ethylene oxide), depending on the particular chain properties. These different dependences have been discussed in terms of: (a) variations of thermodynamic interactions with molecular weight; (b) variations of conformational characteristics (as for instance the ratio) 〈r02/nl2〉, where 〈r02〉 is the unperturbed mean square end-to-end distance and n is the number of bonds each of length l; (c) hydrodynamic properties of short chains.
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  • 43
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1209-1216 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is predicted that the net repulsion between the segments of a polymer network and a poor solvent can cause a phase transition marked by a sudden change in the degree of swelling. This is analogous to the “coil-globule” transition recently predicted by Ptitsyn to occur for a macromolecule in solution. The critical conditions for the transition. as well as phase diagrams, are calculated for the gel in free swelling and under uniaxial tension, which facilitates the transition. The transition depends on the gel being formed of chains crosslinked while greatly swollen by a diluent and also having a high degree of crosslinking. It is concluded that it would be difficult to attain the conditions necessary for the transition in the free-swelling case, but that it should be possible for gel under tension.
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  • 44
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1255-1271 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Morphology and crystal structure of solution-grown and melt-grown crystals of thermally decomposed polypropylene have been studied by electron microscopy and x-ray diffraction. By crystallization from dilute α-chloronaphthalene or carbitol solutions well-defined lamellar crystals about 100-150 A. in thickness are obtained from fractions (number-average molecular weights 1600-2100) of thermally decomposed crystalline polypropylene. The structure is monoclinic as crystallized from very dilute α-chloronaphthalene or carbitol solutions (0.02-0.005 wt.-%). However crystals of the triclinic as well as of the monoclinic forms are precipitated from carbitol solutions of higher concentrations (0.05-1 wt.-%). On the other hand, the separated triclinic form has been obtained from the melt. Crystals of both modifications have similar morphology. In addition, the chain molecules cannot be expected to fold, within the thickness of lamellae in crystals of either modification prepared from the low molecular weight fractions used in this study.
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  • 45
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2009-2019 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With low-shear mixing, a portion of a high molecular weight poly(DMVPMS) is immediately adsorbed, and fairly stable aggregates are formed by the polymer bridging mechanism. The adsorption equilibrium is not established after several weeks because of a very slow liberation of the partly covered surface that is trapped within the aggregates. At a high ionic strength, or when the polymer is degraded to a low molecular weight, the adsorption equilibrium is quickly established because of a weaker bridging in the aggregates. It is proposed that poly(DMVPMS) adsorbs from water in a flattened conformation by an ion exchange mechanism. The saturation level increases and then becomes constant as the ionic strength is increased. Simple electrolytes show a specific effect on the adsorption of poly(DMVPMS) that is analogous to their effect on the interaction of other colloidal particles.
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  • 46
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1-30 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The low-angle light scattering by films of stretched natural and synthetic rubbers was investigated. Intense Vv scattering is found under conditions when crystallization occurs which is characteristic of the scattering from aggregates of dimensions comparable with the wavelength of visible light. These were identified with the γ fibrils described by Andrews. The dependence of scattering was studied as a function of light polarization direction, orientation direction, elongation, temperature, degree of swelling, type of swelling liquid, and degree of crosslinking. It was concluded that the scattering unit consists of an assembly of crystals with their chain axes parallel to the stretching direction, but (in the case of natural rubber at high elongations) with the fibril axis at a slight angle to the stretching direction. The scattering is not affected much by swelling but is decreased upon increasing the temperature. Upon recooling the scattering returns, but does so over several hours, indicating that much of the scattering arises from secondary crystallization.
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  • 47
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 63-89 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Thermodynamic interactions between arbitrarily branched flexible “comb” molecules (with branches of uniform length affixed to backbones of uniform length but with the number of branches on a molecule and their placement arbitrary) are treated by Zimm's perturbation method to obtain results valid to the double contact approximation. Thus, bimolecular cluster configurations with one and two intermolecular contacts, but not more, are correctly accounted for. This general result is applied to “random” combs (with the number of branches per comb uniform, but the placement random) and to “heterogeneous” combs (with both the number of branches on a molecule and their placement random). Results for the random combs are very similar to those reported earlier for “symmetrical” combs (with f uniform branches disposed at points along the backbone chain so as to subdivide it into f + 1 equal sections), but the second virial coefficient for the random model is slightly the larger when the number of branches per chain is small and the fraction of the molecule in the backbone is at least a few per cent. Since random combs are uniform in mass, the osmotic pressure and light-scattering second virial coefficients are alike; but for a system of heterogeneous combs the virial coefficients differ from one another, and from the random comb result, when the mean number of branches f̄ per chain is small and they are of appreciable length in comparison to the backbone. This behavior reflects the heterogeneity in both molecular mass and dimensions existing under these circumstances. As f̄ increases and/or the mean fraction of segments in the chain backbone becomes large, coincidence with the random comb result is approached. The double-contact second virial coefficients for both random and heterogeneous combs are obtained in closed analytical expression that are much more easily reduced to numerical results than the expression for symmetrical combs given earlier. These two models also correspond better than the symmetrical combs to materials actually obtainable.
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  • 48
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 451-456 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A simple statistical thermodynamic argument is presented in which the probability of intramolecular chain folding of normal paraffins and polyethylene in solution is examined. This possibility is based on the existence of low-energy intramolecular conformations which are stable enough to overcome the tendency of a chain molecule to assume a random arrangement in solution. Some rough estimates of the magnitudes of energetic interaction in straight-chain hydrocarbons are made to demonstrate the plausibility of this hypothesis. The experimental support for this model arises from NMR spectra of normal paraffins in aromatic hydrocarbon solvents.
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  • 49
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1227-1240 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A stepwise segment-by-segment cluster development of the interaction energy of two polymer coils at given distance leads to a closed expression, describing the second virial coefficient A2 in terms of certain intersegmental contact probabilities. An approximate expression for A2(α,z) in good solvents is then derived by using the uniform segment cloud model; the result being equivalent to that obtained by Flory. This expression is combined with the author's theory for α2(z) to give A2(z), and then with a subsequent adaptation of that theory to polyelectrolytes, to derive the dependence of A2 on ionic strength. The α2(z) and A2(z) equations are both compared with recently reported experimental data for NaPSS.
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  • 50
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1283-1296 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Isotactic and atactic poly(methyl methacrylate) containing varying amounts of polymerization initiator and chain-transfer additives, and carefully purified radiation-polymerized material, were γ-irradiated in the dark at liquid nitrogen temperature. On warming to room temperature at a near-linear rate of 20°K./min., a glow peak having a maximum luminescence intensity at 162 ± 8°K. was observed in all samples; an additional peak at 239 ± 7°K. was resolved relatively infrequently. Low luminescence yields precluded an investigation of the spectral distribution of the glow peaks. It is shown that the electron traps associated with the lower temperature peak are most probably the main-chain methyl groups, while the higher temperature glow peak is tentatively associated with escape of electrons from structural defects in a few small crystalline regions of the samples. It is postulated that, for the peak at 162°K., the trapped electrons combine radiatively with luminescence centers when thermally induced rotational motion of the main-chain methyl groups permits sufficient wave-function overlap. Assuming that methods of glow curve analysis proposed for inorganic materials are applicable to organics, first-order recombination kinetics and an activation energy of 0.084 ± 0.006 e. v. are deduced for the intensity maximum at 162°K. This activation energy is in fair agreement with that obtained by Bordoni et al. for an unspecified side-chain motion occurring at similar temperatures, but is only about half the values quoted with some reservations by Powles and by Kawai on the basis of NMR experiments. It was not possible to determine the kinetics of the 239°K. peak with certainty, but an activation energy of 0.432 ± 0.085 e. v. follows from a first-order assumption. The additives present in the samples did not appear to play any significant part as electrontrapping agents; this observation contrasts with some recent work on the visible and ultraviolet absorption spectra of the same materials which showed a close correlation of additional bands developed following irradiation with the presence of specific additives.
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  • 51
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1349-1355 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Analysis of polystyrene standards by gel permeation chromatography over a wide range of flow rates revealed two sources of error in volume measurement. These errors arise from solvent evaporation in the siphon chamber and from solvent continuing to flow into the siphon during discharge. Appropriate corrections are discussed, and a vapor feedback loop to eliminate the solvent evaporation error is described. The flow rate dependence of the GPC calibration curve, expressed in the corrected elution volumes, appears different from that reported in the literature. The corrected flow rate dependence of peak elution volumes is in agreement with the expectation of diffusion and exclusion theories.
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  • 52
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1419-1434 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Infrared spectra of methylbutenes and methylpentenes in the skeletal deformation region have been measured. The force constants for the skeletal deformation vibrations are determined from the frequencies of isobutylene, isobutylene-d6, and methylbutenes. The frequencies of methylpentenes are calculated for the various conformations, and the stable rotational isomers determined. The energy differences between the isomers are determined from the temperature dependence of the spectra. These results are correlated with the conformations of cis-and trans-1,4-polyisoprene chains, and possible conformations are suggested.
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  • 53
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1381-1399 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyacrylonitrile crystals were grown from dilute solutions of propylene carbonate by a technique similar to that described by Holland et al. Crystals were also grown on various substrates and sampled at various stages of growth after washing away the uncrystallized solution. The initial single lamellae rapidly develop into complex twinned structures with many overgrowths. The morphology of the full-grown crystal varied considerably with crystallization temperature. Small-angle x-ray and electron microscopy results indicate only a small change in lamellar thickness with crystallization temperature for our polymer. Electron and x-ray diffraction results indicate lateral order can be quite good in these crystals. Our x-ray results indicate that the previously reported a and b parameters should be doubled to give a = 21.18 Å and b = 11.60 Å. However, there was no evidence for chain-axis order. The crystals were stretched at various stages of growth on Mylar film. Multilamellar crystals having their long axis parallel to the draw direction formed large cracks perpendicular to the long axis. Fibers of large diameter (100-250 Å) were observed across these cracks. When the long axis of these crystals was at an angle to the draw direction no large cracks or fibers were observed. Single lamellae generally cracked perpendicular to the draw direction, irrespective of their orientation to the draw direction. Definite fibers were not observable across cracks in single lamellae.
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  • 54
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The shape of the first derivative of the dispersion mode of an inhomogeneously broadened electron spin resonance spectrum changes markedly on saturation. This behavior provides a convenient and rapid technique for estimating the spin latice relaxation time of the paramagnetic species involved. The technique is described together with the relevant theory. Values for the relaxation times of free radicals derived from poly(methyl methacrylate) and from poly(sodium methacrylate) have been obtained by this method and are found to be in good agreement with those obtained by the progressive saturation technique. A series of salts of polymethacrylic acid have been γ-irradiated, and the spin lattice relaxation times of the resulting trapped radicals were determined at 77 and 299°K. For a given polymer the relaxation times show little variation with temperature. This is attributed to a broad distribution of correlation times.
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  • 55
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1561-1566 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A current theory of the tensile strength of rubbers invokes large-scale crosslink interchange at room temperature to explain the high tensile strengths of networks crosslinked with weak linkages. This mechanical lability of certain crosslinks has been assumed from their known thermal lability at higher temperatures. Relaxation of stress experiments at various elongations have been performed at room temperature on networks crosslinked with both weak and strong linkages. Our purpose was to detect mechanically induced crosslink slippage. We have found no evidence of any mechanical lability of weak crosslinks at room temperature. A hypothesis is presented which explains the high tensile strengths of rubbers crosslinked with weak linkages as resulting from an internally relaxed network formed by the thermal lability of the crosslinks at the vulcanization temperature. This theory is shown to be consistent with some previously unexplained experimental results.
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  • 56
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 967-980 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscoelastic properties of uncrosslinked 1,2-polybutadiene (91.5% vinyl, 7.0% cis, 1.5% trans, number-average molecular weight 99,000) were studied by dynamic shear measurements between 0.15 and 600 cps (torsion pendulum and Fitzgerald transducer) and shear creep measurements over time periods up to 3.7 × 104 sec., in the temperature rang from 5 to 50°C. More limited dynamic measurements were made on a sample of unvulcanized natural rubber with number-average molecular weight 350,000 at frequencies from 0.4 to 400 cps and temperatures from 13 to 48°C. All data were reduced to 25°C. by shift factors calculated from equations of the WLF form with the following coefficients: 1,2-polybutadiene, c1 = 6.23, c2 = 72.5; natural rubber, c1 = 5.94, c2 = 151.6. In the transition zone, the relative positions of the loss tangent curves on the logarithmic frequency scale for these and other rubbers (1,4-polybutadiene with 50% trans configuration; styrene-butadiene rubber with 23.5% styrene content; and polyisobutylene) provided relative measures of local segment mobility. At 25°C., these ranged over a factor of 3700 with 1,2-polybutadiene and polyisobutylene the lowest and 1,4-polybutadiene the highest. When the frequency scale of each rubber was reduced to a temperature 100°C. above its glass transition temperature, however, the loss tangent curves for all except polyisobutylene were nearly coincident; the latter still showed a lower mobility by a factor of about 1/800. The terminal relaxation time and steady-state compliance for the 1,2-polybutadiene calculated from the Rouse theory were larger than those observed experimentally. The level of compliance corresponding to the entanglement network of 1,2-polybutadiene, JeN, was calculated by integration over the loss compliance, J″, to be 1.62 × 10-7 cm.2/dyne; integration over G″ to obtain the corresponding modulus gave reasonable agreement. From such JeN, values, the average number of chain atoms between entanglement points, jZe, was estimated as follows: 1,2-polybutadiene, 132; natural rubber, 360; 1,4-polybutadiene, 110; styrene-butadiene rubber, 186; polyisobutylene, 320. Values of jZe were also estimated from the minimum in the loss tangent and compared with those reported from the molecular weight dependence of viscosity. The three sources were in generally good agreement.
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  • 57
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1639-1648 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The steady-state current density versus applied electric field characteristics have been measured for two types of polystyrene films. Measurements were made on 1-mil biaxially oriented film and on films produced by casting from solution. The cast films ranged from 5 to 0.5 μ in thickness. The measurements of the steady-state current flowing through the films were done by two different methods. The first was the direct observation of current flowing in a circuit connected to the film which was under a potential stress. The second involved the observation of the decay of a static charge placed on the surface of a film. Both methods are handicapped by the fact that large transient currents flow for extended periods after any change is made in the experimental set up. The results indicate that at 25°C the current increases as the 3.5 power of the applied electric field when the field is greater than 8 × 104 V/cm. At fields less than 8 × 104 V/cm the current decreases more rapidly and tends to become zero.
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  • 58
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1093-1100 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An investigation has been carried out of the interaction of optically active tris(ethylenediamine)-Co(III) and of tris(o-phenanthroline)-Ni(II) complex ions with different polyelectrolytes in dilute aqueous solution. Optical rotatory dispersion measurements reveal that binding of the Co(III) complex ions occurs with a noticeable degree of specificity which in addition to depending on the nature of the fixed charges is also affected by the chemical constitution of the polyelectrolytes chain backbones. The dependence of tris(ethylenediamine)-Co(III) optical activity on polyelectrolyte concentration also exhibits interesting features. Polarimetric measurements of the rate of racemization of tris(o-phenanthroline)-Ni(II) ions in the presence of different polyelectrolytes lead to similar conclusions. Sodium dextran sulfate is shown to interact selectively with one of the antipodes of tris(phenanthroline)-Ni(II) complex.
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  • 59
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1161-1175 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The melt viscosity, the glass transition, and the effect of pressure on these are analyzed for polystyrene on the basis of the Tammann-Hesse viscosity equation: log η = log A + B/(T - T0). Evidence that the glass transition is an isoviscosity state (log ηg ≃ 13) for lower molecular weight fractions (M 〈 Mc) is reviewed. For a polystyrene fraction of intermediate molecular weight (M ≃ 19,000; tg = 89°C.), it is shown that B is independent of the p-v-T state of the polymer liquid and that dT0/dP = dTg/dP. This is consistent with the postulate that B is determined by the internal barriers to rotation in the isolated polymer chain. Relationships are derived for flow “activation energies” at constant pressure and at constant volume, and for the “activation volume.” Values for polystyrene along the zero-pressure isobar and along the constant viscosity, glasstransition line are reported. For the latter, ΔVg* is constant and corresponds to about 10 styrene units. The “free volume” viscosity equation: log η = log A + b/2.3φ, is reexamined. For polystyrene and polyisobutylene, φg/b = 0.03, but φg and b themselves differ appreciably in these polymers. The parameter b is the product of an equilibrium term Δα and the kinetic term B, and none of these is a “universal” constant for different polymers. The physical significance of the free volume parameter φ, particularly with regard to the “excess” liquid volume, remains undefined. Two new relationships for dTg/dP, one an exact derivation and the other an empirical correlation, are presented.
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  • 60
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1810-1812 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 61
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1853-1861 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A theoretical treatment is given for the formation of visible holes in an elastic solid. It differs from previous treatments of bubble formation in liquids by neglecting the problem of hole nucleation altogether. Instead, a small spherical hole is assumed to be present initially. The inflation of such a hole by a dissolved gas is then considered. A critical internal pressure is deduced, at which the hypothetical hole would become infinitely large. This pressure is given by 5G/2; where G is the shear modulus of the rubber. Some model experiments are described in which swollen rubber vulcanizates were rapidly heated to bring the dissolved liquid into a superheated conditions. The temperatures of rapid bubble formation were determined for a number of vulcanizates having different degrees of crosslinking and hence different values of shear modulus, and for different swelling liquids. The results are shown to be in reasonably good quantitative agreement with the theoretical predictions.
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  • 62
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1933-1934 
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    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 63
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1938-1942 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 64
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1945-1952 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The structure of the polycarbonate chain has been analyzed from the point of view of the spatial configurations it may assume. The carbonate group is certainly planar, and the trans,trans configuration probably is strongly preferred. Rotations about the aryloxygen bonds are subject to symmetric, twofold potentials. It follows that the molecule can be treated as a freely rotating chain consisting of a succession of virtual bonds 7.0 Å in length, joined at angles of ca. 112°. Calculations carried out on this basis yield 〈r2〉0/M = 0.85 Å2/g-mole wt for the unperturbed random coil, in excellent agreement with the experimental results of Berry, Nomura, and Mayhan. The effect of occurrence of some of the carbonate groups in cis, trans configurations is investigated using more elaborate methods.
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  • 65
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1999-2007 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A brief description is given of a new parallel-plate rheogoniometer for normal stress measurements on polymer melts as functions of the rate of shear. A wire-resistance strain gauge is used as the pressure gauge. Measurements are reported on high-density polyethylene. It is found that the time-temperature superposition principle is applicable to the normal stress data as well as to shear stress in steady flow.
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  • 66
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 2067-2070 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 67
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1649-1658 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The surface of thin polyethylene films (ca. 1 mil) nucleated on high- and low-energy surfaces was studied. It was found that the degree of crystallinity in the surface region, as determined by transmission and reflection infrared spectroscopy, was dependent on the nature of the substrate. Relatively small and randomly oriented spherulites were observed in the surface region of thin polyethylene films nucleated on gold, a high-energy surface. The surface region of a thin polythylene film nucleated on polytetrafluoroethylene, a low-energy substrate, was observed to have considerably fewer spherulites, but much larger in size, with orientation restricted, in general, to the plane of the film. The relative intensity of the 720 cm-1 to the 730 cm-1 band in the reflectance spectra (ATR) indicates that the surface region of a polyethylene film nucleated on a high surface energy substrate is more crystalline than the surface region of a film nucleated on a low surface energy substrate.
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  • 68
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1686-1688 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 69
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1733-1745 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The orientation of the crystallographic c axis (chain axis) was followed by x-ray diffraction during the crystallization of four samples of isotactic polystyrene differing in elongation ratio. The crystallite orientation can be expressed by 〈cos2 χc〉, where χc is the angle between the c axis and the stretching direction. The degrees of crystallinity w were estimated from the diffraction data by using density for calibration. It was found that 〈cos2 χc〉 decreases in a linear manner with crystallinity, the rate of decrease being very small when the elongation ratio α is 5, but becoming progressively larger as α is decreased toward unity. A qualitative measure suggests that amorphous orientation decreases during crystallization at a rate which is nearly independent of α. The variation of 〈cos2 χc〉 with w is therefore governed by the orientation of the statistical chain segments prior to crystallization. If the elongation ratio is small, the supply of well oriented statistical segments is limited, and 〈cos2 χc〉 will decrease at a rapid rate during crystallization. A treatment due to Krigbaum and Roe permits evaluation of the ratio, ν/N, where ν and N are the average numbers of statistical segments in the crystallization nucleus of critical size, and in a network chain, respectively. Our polystyrene samples were not crosslinked, so chain entanglements must serve as junction points. Values of ν could not be obtained, since N was unknown. However, the (ν/N) ratio for isotactic polystyrene decreases slowly with α, and the values agree reasonably well with those obtained in a previous study of oriented polychloroprene networks. After nearly complete crystallization (ω ca. 0.30), the long period spacing measured by low angle diffraction was approximately 135 Å, and varied only slightly with elongation ratio in the range α = 1 to 5. It therefore appears that chain folded lamellae are present in both drawn and undrawn samples of isotactic polystyrene.
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  • 70
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 31-61 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A fluorocarbon copolymer of chlorotrifluoroethylene (96%) and vinylidene fluoride has been isothermally crystallized and the quenched films analyzed by the light microscope, photographic light-scattering, and density measurements. Above a supercooling of 79°C., homogeneous nucleation dominates, giving a morphology that appears to be that of a twisted ribbon. At supercoolings below 79°C., heterogeneous nucleation dominates and leads to spherulitic morphology. Sheaf or rodlike morphology occurs at very low supercoolings. Crystallization rates determined from density measurements at room temperature indicate maximum rate due to heterogeneous nucleation occurring at a supercooling greater than 79°C., but the temperature for maximum rate cannot be identified because of the transition to homogeneous nucleation which causes a discontinuity in the rate versus temperature curve. Superposability of crystallization isotherms constructed from density values are inconsistent with the large melting point lowering from that of polychlorotrifluoroethylene for this copolymer. However, this may be explained by the presence of a different crystal system for each monomer in the copolymer.
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  • 71
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 165-180 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The spherulitic growth data that exist in the literature for a wide diversity of polymers have been analyzed according to various possible nucleation mechanisms. It is demonstrated that, if allowed a reasonable choice for the equilibrium melting temperature, no unbiased selection of a unique nucleation process can be made. Moreover, a set of universal parameters exists for each of the allowable nucleation processes which enables the data to be represented by a single straight line which encompasses all the polymers. The only quantities specific to a given polymer are the equilibrium melting temperature and the activation energy for transport. The magnitude of the latter quantity is shown to be dependent on the glass temperature of the polymer.
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  • 72
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 241-248 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polyoctadecene-1, as isolated from a Ziegler-type polymerization, was examined by density and refractive index measurements and by differential thermal analysis. Two main transitions were observed, their sharpness suggesting that they are both first-order. Extraction with n-hexane at 25°C. separated the polymer into two almost equal fractions, each showing essentially one of these transitions. Transition temperatures were compared with those of certain other polymers having long n-alkyl side chains. From this comparison, and from the findings of other workers, it was concluded that the polymer of lower transition temperature is atactic polyoctadecene, in which the side chains only participate in crystallization, whereas the polymer of higher transition temperature is tactic polyoctadecene, in which crystallization involves both the main chain and side chains.
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  • 73
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 249-257 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: On the basis of an isoviscosity criterion for the glass transition (ηg ⋍ 1013 poise) in liquids of low molecular weight, theoretical Tg values were calculated for the n-alkane series by the equation log η = log A + B/(T - T0), with the use of values reported by Lewis for the parameters. The Tg/T0 ratio reaches a limiting value of 1.25 and φg = (Tg - T0)/2.3B = 0.027, a constant. Extrapolation to (CH2)∞ gives Tg = 200°K., T0 = 160°K., and B = 640°K. This Tg is consistent with other estimates for poly-ethylene, and T0 coincides with the temperature at which the “excess” liquid entropy for (CH2)∞ becomes zero from thermodynamic data. For polymer liquids it is proposed that E0 = 2.3RB is determined by the internal barriers to rotation for the “isolated” polymer chains. Thus, E0 = 2.9 kcal./mole for polyethylene, 3.0 kcal./mole for polystyrene, 5.7 kcal./mole for polyisobutylene, and 1.9 kcal./mole for polydimethylsiloxane.
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  • 74
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 265-279 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ESR spectra of peroxy radicals in irradiated powders and oriented samples of polytetrafluoroethylene (PTEE) have been measured with a K-band spectrometer, and the principal values and directions of the g tensor were determined both at room temperature and at 77°K. In contrast to the spectra of the usual peroxy radicals, those trapped in γ-irradiated PTFE exhibited an ESR spectrum apparently having a larger principal value for g⊥ than for g∥ when measured at room temperature, although the normal principal values were observed at 77°K. As for the directions of the principal axes, g∥ was directed along the chain axis at room temperature and was perpendicular to the chain axis at 77°K. From the temperature change of the g tensor and the line shapes in the oriented samples, it is shown that the observed temperature change of the spectra is due to rapid rotation at room temperature around the chain axis rather than around the C—O bond axis. Assuming this, the apparent principal values of the g tensor at room temperature were calculated from the g tensor obtained at 77°K. for the rigid state, and the results are in good agreement with observations at room temperature. A structure for the peroxy radicals is also proposed. In addition, the spectral line shape function for the uniaxially oriented samples has been derived.
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  • 75
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 294-299 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 76
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 325-347 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Theoretical and experimental evidence is put forward to prove that the determination of the phase-volume ratio as a function of temperature and concentration is a sensitive and simple means of determining the liquid-liquid critical state. Knowledge of the critical conditions permits very accurate calculations of the interaction parameter g in the free-energy function. In experiments with polystyrene-cyclohexane, g was found to depend on the concentration. The value of g and its concentration dependence agree very well with the results of osmotic measurements by Rehage and Palmen. In experiments with polyethylene-diphenyl ether, g proved to be independent of concentration in the range of measurement. The temperature function was found to be: g = -0.6086 + 482.2/T (at 137-148°C.). Gibbs' expressions for the critical conditions were worked out for a free-energy relation in the form of an extended Flory-Huggins function.
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  • 77
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 349-366 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Cloud-point curves (CPC) were calculated on the basis of the Flory-Huggins free-energy relation for various hypothetical polymer samples dissolved in a single solvent. Molecular weight distributions varying widely in shape and width were examined. The shape of the CPC reflects details of the molecular weight distribution. This appears from the location of the critical point on the right-hand branch of the CPC. The latter often shows a depression, which becomes more distinct as the Mz/Mw value increases. These theoretical results were confirmed experimentally with the system polyethylene-diphenyl ether. With the aid of the theoretical data collected it was possible to explain the remarkable agreement between the θ temperatures determined by light-scattering and by the Shultz-Flory method. The latter method is basically incorrect, since it identifies the polymer solution with a binary mixture. An explanation could also be given for the empirical relation which McIntyre et al. recently found between the shape of the top of the CPC and the width of the molecular weight distribution.
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  • 78
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 421-431 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The electric birefringence of sodium polyethylenesulfonate in water has been studied. For a low molecular weight fraction, the electric field dependence followed the Kerr law quite closely. For a higher molecular weight fraction, the specific Kerr constant was much larger, and pronounced saturation of the electric birefringence was observed in fields of 15 kv./cm. The specific Kerr constant increased with decreasing polyelectrolyte concentration in pure water. On the other hand, it decreased on isoionic dilution. The saturation effect was the more marked, the lower the polyelectrolyte concentration. The saturation behavior resembled that of permanent dipole orientation, but this mechanism was not supported by the build-up of the birefringence. The magnitudes of specific Kerr constants of various types of macromolecules in solution are tabulated and discussed.
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  • 79
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of measurement of the shear and tensile creep compliance of poly(methyl methacrylate) between -150 and 75°C. are presented. The master curves show the creep behavior from essentially elastic response to the onset of the α-process. The logarithmic retardation spectra and shear loss compliance reveal two molecular processes, one process being partially obscured by the α-process and therefore not as well defined as the other. These processes manifest themselves as breaks in an Arrhenius plot of the shift factors at about -35 and +25°C. The activation energies in the -35 to 25°C. and 25 to 80°C. ranges are 17.8 kcal./mole and 42.2 kcal./mole, respectively. The former temperature range and activation energy corresponds to the well-known ß-process in poly(methyl methacrylate), the latter to a process which is apparently detectable using various long-time experimental techniques but whose molecular interpretation is at present obscure. The activation energy in the -150 to -35°C. range is about 8.7 kcal./mole.
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  • 80
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 493-498 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Nuclear magnetic resonance of poly-β-alanine samples differing in solubility in water was studied over a wide temperature range as part of an investigation of their physical properties. Water-soluble poly-β-alanine has more branches and a lower degree of crystallinity than water-insoluble poly-β-alanine. NMR spectra of poly-β-alanine show one component at 77°K. which splits into two components, broad and narrow, at room temperature. Two transition regions were observed in curves for line width and second moment versus temperature. The higher transition temperature, corresponding to the glass transition of the polymer, appears to decrease with increasing water content. The second moment for the water-soluble polymer differs from that of the water-insoluble polymer at 77°K. This is interpreted in terms of the difference in the degree of crystallinity of the polymers.
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  • 81
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 479-492 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Viscoelastic properties of four linear and three very lightly crosslinked polybutadienes (microstructure about 50% trans) were studied. Of the latter, two had not reached the gel point, and their molecular weight distributions were determined by sedimentation velocity analysis; the third was crosslinked just past the gel point, with only 32% gel fraction present. The crosslinking agent was sulfur. Complex shear compliances were measured over a frequency range from 0.1 to 1000 cps at temperatures from -70 to 30°C. with a Fitzgerald transducer and a Plazek torsion pendulum; and torsional creep measurements were made over time periods up to about three days. The creep data were converted to the corresponding dynamic viscoelastic functions at very low frequencies by conventional approximation methods. All data were reduced to 25°C. by shift factors calculated from a previously adopted equation of the WLF form. In the transition zone, the viscoelastic properties of linear samples were almost independent of molecular weight. The entanglement spacing, derived from the minimum in the loss tangent and the inflection in the storage compliance, was 130 to 160 chain atoms. The maximum in the retardation spectrum attributable to motions of individual network strands was closely similar to the corresponding maxima for more highly crosslinked vulcanizates previously studied, showing that even in the latter it is associated with entanglement network strands rather than strands between chemical crosslinks. For a linear sample with molecular weight 180,000, the retardation processes disappear at times beyond about 10 sec. at 25°C. With crosslinking short of the gel point (i.e., branching) the slow retardation processes are enormously increased and prolonged to longer times. With further crosslinking through the gel point and beyond, the slow retardation processes decrease progressively in magnitude. Qualitatively, this behavior resembles the sharp maximum in content of highly branched and aggregated molecular species which is predicted at the gel point by crosslinking statistics; but the slow processes (or low-frequency losses) persist farther past the gel point than would be expected on this basis. The steady-state compliances of the linear samples were smaller, but for a sample crosslinked short of the gel point were much larger, than the prediction of the Rouse theory modified for molecular weight distribution.
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  • 82
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 575-585 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of the intrinsic viscosity [η] for the system polystyrene-cyclohexane in the interval -20 〈 (T - ψ) ≤ 0 near the ideal temperature ψ has been investigated. The observed diminution in size of the molecular coil with decreasing temperature is attributable to attractive net polymer-solvent interactions, denoted by negative values for the excluded volume parameter z. The data thus comprise an interesting selection for comparison with the predictions of various excluded volume theories. Among the approximate, closed-form expressions the functional relationship of Flory (x5 - α3 ∼ z) appears to describe best the variation of [η] with temperature in the region examined. The behavior of the Huggins constant k′ derived from the intrinsic viscosity plots is also examined, in accordance with the Peterson-Fixman model, suitably extended to the temperature region below ψ.
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  • 83
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 559-574 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The product of the thermal polymerization of ß-carboxymethyl caprolactam has been identified as a poly[(2,6-dioxo-1,4-piperidinediyl)trimethylene]. An indication of various chain conformations has been explained by the possible existence of two different conformations of the dioxopiperidine moiety. One conformation pertains to an equatorial position of the trimethylene moiety with respect to the plane of the imide group. The other is derived from a structural unit in which the trimethylene group is positioned axially to the plane of the ring. While the former conformation has been ascribed to the crystalline modification the latter appears to be the predominant structure of the polymer in formic acid solution as indicated by NMR analysis. In the glassy state the macromolecule is assumed to be composed of segments of either conformation. The unoriented linear polymer crystallizes upon annealing in positively birefringent spherulites. A triclinic unit cell with the following parameters: a = 9.64 A., b = 11.32 A., c = 15.80 A., α = 98°, β = 96°, γ = 114° has been found to contain eight structural units. The calculated density, 1.30 g./cm.3, agrees with experimental data. A crystal structure is proposed on the basis of the x-ray data.
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  • 84
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 587-605 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Drawn PE of different draw ratios (ranging from 1 to 25) and thermal treatment (annealing temperature 80, 100, 110, 120, 127°C.) was treated with fuming nitric acid at 80°C. Weight loss, molecular weight, elastic modulus, and thermograms were measured for annealed and unannealed samples as a function of the treatment time and draw ratio. As a consequence of the preferential oxidation of the noncrystalline portions, there occurs initially a high rate of weight loss and a steep drop in molecular weight, followed by a lower rate of weight loss at nearly constant molecular weight. The elastic modulus stays practically constant up to the moment where the brittleness of the sample prevents further measurement. During the later period the thermograms exhibit one melting peak during the first melting. The remelt of the same sample, however, has two melting peaks with a relative intensity independent of the treatment time. That the two melting peaks are caused by two components of different molecular weights present in the sample is substantiated by fractionation. At very high annealing temperature (127°C.), two peaks appear, not only in the first melting curve of the etched sample, but also in the melting curve of the unetched material. Such an effect is the consequence of partial melting during annealing followed by new crystallization during cooling the sample to room temperature. The findings are related to the morphology of the drawn material under the assumption of preferential scission of chain loops in the amorphous-crystalline sandwich layer model.
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  • 85
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 653-656 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
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  • 86
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 687-694 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The results of an investigation of the viscoelastic and thermal properties of the gelatin-glycerol system are presented in the form of a complete temperature-composition diagram. This diagram shows the isochronal (10-sec.) mechanical behavior of the system along lines of constant modulus and thereby affords a convenient assessment of variation in viscoelastic behavior along any isotherm or isopleth of interest. Comparison of the results with previously obtained limited sets of data on a number of other polymer-dilent systems indicates the applicability and utility of such a presentation.
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  • 87
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 707-712 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: It is reported that mats formed by the sedimentation of single crystals of methyl- and ethyl-branched polyethylene exhibit strength and ductility comparable with that of melt-crystallized films. In fact, in the case of methyl-branched polymers, extensions of up to 50× were obtained on cold drawing. Observations on separate crystals suggest that this extension is due to the pulling out of individual lamellae. In view of the magnitude of the extension, this implies unfolding of the molecules. That considerable coherence can be obtained without original molecular ties between crystals is of significance as regards the molecular interpretation of the strength and ductility of crystalline polymers.
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  • 88
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 735-744 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The unperturbed mean-square end-to-end distance 〈R02〉 and its temperature variation d In 〈R02〉/dT for isotactic polypropylene have been estimated from intrinsic viscosity data in three theta solvents, i.e., diphenyl, diphenyl ether, and dibenzyl ether, measured at their θ temperatures as determined by precipitation temperature measurements. The characteristic ratios, 〈R02〉/nl2, where n is the number of bonds of length l in the main chain, evaluated by assuming Φ = 2.87 × 1021, are 5.80 in diphenyl (at θ = 125.1°C.), 5.41 in diphenyl ether (at θ = 142.8°C.), and 4.56 in dibenzyl ether (at θ = 183.2°C.). These values lead to the temperature coefficient d In 〈R02〉/dT = -4.09 × 10-3 deg.-1 Results are compared with the data previously reported on polyethylene.
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  • 89
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When cellulose triacetates and some hydrolyzed acetates are boiled in 2.5N hydrochloric acid there is no residue. Under the same conditions cellulose is hydrolyzed, and a residue is obtained with a limiting viscosity that is related to the average length of the cellulose crystallites. These findings are combined to develop a method for studying the progress of acetylation through the amorphous portion of cellulose and into the crystallites, and to investigate the relative reactivities of cellulose I and cellulose II. Acetates were made from cotton and wood cellulose by a “fibrous” (heterogeneous) esterification involving sulfoacetic acid or perchloric acid catalyst in acetic acid-acetic anhydride; the final acetyl contents (10-41%) were attained by stopping the reaction at various points short of the triester (rather than by hydrolyzing a triester). When these acetates were boiled in 2.5N HCI they did not disappear completely, and the residues were cellulose I, indicating that cellulose acetate had been removed. With increasing acetyl the yield of residue decreased, and beyond about 33% acetyl the viscosity and x-ray measurements showed that the length and width of the crystallites decreased. However, when a nonsolvent such as toluene was added to the acetylation medium, the limiting viscosity did not change over the same acetyl range (up to 40%). Samples of varying acetyl values were taken during a regular acetylation of cotton linters in a mixer with sulfuric acid catalyst. X-ray studies of the residues obtained by boiling the acetates in 2.5N HCI revealed the presence of unreacted cellulose I even after 40% acetyl had been reached. This explains why the manufacture of cellulose esters from cellulose I requires complete esterification before they are hydrolyzed to the desired acetyl level. It was shown that there is a distinct difference between the acetylation reactivity of cellulose I and cellulose II. This indicates the importance of avoiding cellulose II formation during the refinement of cellulose for the manufacture of cellulose acetate in a process involving activation with acetic acid.
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  • 90
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 813-823 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The phase equilibria in polymer-liquid 1-liquid 2 ternary systems have been calculated on the basis of the Flory-Huggins theory of polymer solutions. A new approximation method based on the “cluster” concept has been introduced for mixed solvents comprising a solvent and a nonsolvent. This concept has been verified with polystyrene-solvent-methanol systems.
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  • 91
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 833-848 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Highly crystalline polycaprolactam was prepared by zone polymerization of ε-caprolactam. Folded-chain crystallized and annealed, melt-crystallized, and solution-crystallized polycaprolactam was produced from commercial polycaprolactam. All samples were characterized by x-ray diffraction, electron microscopy, density measurement, and heat of fusion measurement. The determination of the time-dependent melting by DTA and scanning calorimetry revealed that all the different morphologies show different melting behavior. Zone-polymerized polycaprolactam superheats, and the other morphologies reorganize on heating to different degrees. Densities and heat of fusion vary in the same manner - from highest to lowest - in the order: zone-polymerized, solution-crystallized, annealed, and melt-crystallized. An estimate of heat of fusion, equilibrium melting point, and surface free energy was obtained from the melting points.
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  • 92
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 849-860 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Precise heat capacity values are reported over the temperature range from 10 to 360°K. for a sample of atactic polystyrene having a narrow molecular weight distribution. This sample was taken from the stock from which National Bureau of Standards Standard Sample 705, Narrow Molecular Weight Distribution Polystyrene, was established. Data are reported for the sample as received, and after an annealing procedure. At temperatures below about 60°K. a systematic difference comparable with the limits of experimental precision appears between the values obtained for the present sample as received and after the annealing, although at higher temperatures the values for the two conditions showed no systematic difference beyond the limits of precision of the measurements. At temperatures above 100°K., previously published values for atactic polystyrene samples of various molecular weight distributions and for isotactic polystyrene agree within about 0.5% of the values from this investigation. At temperatures below 100°K. significant heat capacity differences appear, especially between values for the atactic and the isotactic isomers, and even between atactic samples of different molecular weight distribution.
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  • 93
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 94
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 921-932 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanical effects of association between pendant ionic groups are investigated in series of butadiene-lithium methacrylate copolymers, butadiene-methyl (2-methyl-5-vinyl)-pyridinium iodide copolymers, and mixtures of these polyelectrolytes. Thermal and mechanical tests reveal a new transition above Tg in the pyridinium copolymers, designated Tt*. Below this temperature the materials behave like covalently crosslinked elastomers. The complex between the metal carboxylates appears thermally dissociable at all temperatures. The mixing of the oppositely charged polyelectrolytes leads to the formation of more stable intermolecular pyridinium carboxylate links.
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  • 95
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 995-1010 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The vibration frequencies of a polyethylene crystal lattice have been computed for various structures in which a fully deuterated chain is mixed with a normal chain. Intermolecular potential functions previously developed by the authors were used in the calculation. It is shown that such structures make it possible to distinguish experimentally between chain folding in the (110) plane and folding parallel to the (100) plane. Calculations have also been done for a regular polymer of (CH2CD2). Such a structure would permit the determination of the parity of the number of methylene groups in the fold.
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  • 96
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1011-1020 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: With an increasing gradient, the intrinsic viscosity of a high molecular weight polyisobutylene (M̄n = 7 × 106) in polybutene oil L.100 (ηs = 5 poise) first drops to a minimum and then rises again. The minimum occurs at β = M[η]0ηsG/NkT = 240, which is about ten times the value predicted by the dumbbell model. Such a shift to larger gradient is in good agreement with the more realistic necklace model of macromolecules in a good solvent. The increase of intrinsic viscosity after the minimum is nearly linear with the gradient and continues beyond the value at zero gradient. Experiments with capillaries of different length-to-diameter ratios yield identical flow curves so that one may exclude the possibility that the observed upturn is an artifact caused by end effects or time dependence of viscosity.
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  • 97
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 1021-1033 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Depolymerization of amorphous polyacetaldehyde has been studied by measurements of weight loss versus time for thin films of the polymer in vacuum. Temperatures ranged from 40 to 80°C. The samples were prepared by freezing or melting the monomer in contact with treated glass surfaces. Light scattering, osmometry, and intrinsic viscosity measurements were used to characterize the polymers. Depolymerization rates were between second and third order with respect to the unvolatilized fraction, and the activation energy was 26.3 kcal. Much of the evidence points toward a slow unzipping reaction at the chain ends, but the analysis seems to be complicated by structural variations among the samples.
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  • 98
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 723-733 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Phase relationships of isotactic polypropylene in various organic diluents were investigated. The diluents used were aliphatic alcohols, alkyl phenols, aryl phenols, diphenyl derivatives, alkyl aryl ethers, esters, and others. Among the diluents examined, n-butyl alcohol, p-tert-butyl phenol, p-tert-amyl phenol, diphenyl, diphenyl ether, benzyl phenyl ether, dibenzyl ether, and benzyl propionate were found to be theta solvents for isotactic polypropylene at temperatures in the range 120-190°C. For these theta solvents, the thermodynamic interaction parameters were determined. The results are discussed in relation to the type of diluent.
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  • 99
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 775-782 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Droplet experiments have been performed on polybutene-1. It was found that this polymer can be cooled to room temperature without homogeneous nucleation of crystallization. It was also found that when the polymer was heterogeneously nucleated, form I (as well as form II) could be crystallized directly from the melt. The melting point of droplets crystallized in form I near room temperature decreased with increasing crystallization temperature, while the melting point of the droplets crystallized in form I at the highest temperatures increased with increasing crystallization temperature. There was a broad minimum at about 60°C. in the melting point versus crystallization temperature curve.
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  • 100
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    Journal of Polymer Science Part A-2: Polymer Physics 6 (1968), S. 787-793 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Time-temperature superposition can be successfully applied to both the stress relaxation and dynamic mechanical properties of oriented PET fibers. Two curves result; one is the time dependence of the modulus at constant temperature, while the other is the shift, log aT, of this curve along the time scale as a function of temperature. This temperature dependence is less than that for both unoriented PET and typical amorphous polymers above Tg. It is about the same as that for oriented nylon 66 and unoriented glassy poly(methyl methacrylate). The isothermal modulus has the same time dependence as that of the unoriented PET; however, it is a factor of 3.3 larger. The modulus curve is almost identical in both shape and magnitude with that of oriented nylon 66. However, a temperature of 82°C. is required to place the viscoelastic dispersion region of PET at the same time scale as nylon 66 at 25°C. This temperature increase is the major difference in viscoelasticity between these two oriented polymers.
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